Biocide compositions comprising carbamates

ABSTRACT

Described are biocide compositions, comprising (a) carbamates, (b) biocides and optionally (c) oil components/co-solvents and/or (d) emulsifiers. The compositions have high solubility for biocides and improved emulsification properties.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is the National Stage entry of PCT/EP2010/006792, filed on Nov. 8, 2010, which claims priority to European Patent application number 09014325.6, filed on Nov. 17, 2009, both of which are incorporated herein by reference in their entireties.

TECHNICAL FIELD

The present invention relates to the area of agrochemicals and refers to biocide compositions comprising certain carbamates and their use as solvents or dispersants for biocides.

BACKGROUND

Biocides, and in particular pesticides such as fungicides, insecticides and herbicides, are important auxiliary agents for agriculture in order to protect and to increase crops yields. Depending on the various and often very specific needs a magnitude of actives exist which show very different chemical structures and behaviours. Nevertheless, it is known that it remains difficult to prepare concentrates of these actives which are exhibiting a satisfying stability, especially if stored at very low or elevated temperatures over a longer period.As a matter of fact, the solutions show a strong tendency to either separate or to form crystals, which makes it necessary to re-disperse the actives in the compositions prior to every application in order to obtain a homogenous product. Due to the fact that in spray equipments, which are customarily used for the application of aqueous formulations of plant treatment agents, several filters and nozzles are present, an additional problem appears which is related to the blocking of these filters and nozzles as a result of crystallizing active compound during the application of aqueous spray liquors based on solid active compounds.

European patent application EP 0453899 B1 (Bayer) discloses the use of carbamates derived from saturated C₆-C₂₀ fatty acids as crystallisation inhibitors for azole derivatives which can be applied as fungicides. German patent application DE 4112873 A1 discloses a composition comprising a fungicide (triflorine), lactic acid dimethyl amide and an emulsifier.

Products generally found in the market present either a limited content of biocides and for hazardous labelling and a non favourable eco-tox profile.

The problem underlying the present invention has been to identify suitable new solvents for developing new biocide compositions with equal or higher contents of actives than obtainable in the market. The new solvents need to be safe and environmental friendly and should allow obtaining concentrated biocide compositions (on average more than 15% active matter) regardless of the chemical structure of the biocide, in other words they need to be excellent solvents for a wide range of herbicides, insecticides and fungicides. Finally, another object of the invention has been to design emulsifiable concentrates formulations with specific co-solvents and emulsifier system providing superior emulsion stability, in particular with respect to opacity and layering.

SUMMARY

Embodiments of the present invention are directed toward a biocide composition comprising a carbamate, a biocide, and, optionally, an oil component/co-solvent and/or emulsifier.

In one or more embodiments, the carbamate is a compound represented by R²R³—N—(C═O)O—R¹, wherein R¹ stands for HO(CH₂)_(n) or CH₃ (CH₂)_(m)OH, m and n both represent independently integers of 3 to 22, R² and R³ independently represent hydrogen or alkyl groups having 1 to 12 carbon atoms, optionally forming a ring system.

In one or more embodiments, the carbamate is derived from ethylene carbonate or propylene carbonate.

In one or more embodiments, the biocide is selected from the group consisting of herbicides, fungicides, insecticides, and plant growth regulators. In a specific embodiment, the biocide is selected from the group consisting of azoles, oxyfluorfen, propanil, chlorpyrifos, bifenthrin, novaluron, phenmedipham, deltamethrin, acetochlore, lambda-cyhalothrin, glyphosate and their salts, glufosinate and their salts, and their mixtures.

In one or more embodiments, the oil component/co-solvent is selected from the group consisting of Guerbet alcohols based on fatty alcohols having 6 to 18 carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear or branched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylic acids with linear or branched C₆-C₂₂-fatty acids with branched alcohols, esters of C₁₈-C₃₈-alkyl hydroxyl carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols and/or Guerbet alcohols, triglycerides based on C₆-C₁₀-fatty acids, liquid mono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters of C₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, esters of C₂-C₁₂-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C₆-C₂₂-fatty alcohol carbonates, Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of monopropylene glycol with C₂-C₁₈ acids and benzoic acid, esters of benzoic acid with linear and/or branched C₆-C₂₂-alcohols, linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons, mineral oils and their mixtures.

In a specific embodiment, the oil component has an ester structure. The oil component can be selected from the group consisting of adipates, methyl esters of vegetable oils, and alkyl esters.

In one or more embodiments, the emulsifier is selected from non-ionic and/or anionic surfactants.

In one or more embodiments, the composition comprises 0.1 to 99% by weight based on the composition a carbamate, 1 to 99.1% by weight based on the composition a biocide, 0 to 50% by weight based on the composition an oil component/co-solvent, and 0 to 15% by weight based on the composition an emulsifier, wherein the components add optionally together with water to 100% by weight based on the composition.

Other embodiments of the present invention are directed a method of preparing a biocide, the method comprising using a carbamate as a green solvent or dispersant.

DETAILED DESCRIPTION

The present invention provides for a biocide composition, comprising

(a) a carbamate,

(b) a biocide, and optionally

(c) an oil component and/or co-solvent

(d) an emulsifier.

Surprisingly it has been observed that carbamates, in particular those obtained from reaction between carbonates and amines are efficient solvents/co-solvents for pesticide. For example, a carbamate showing the formula (I)

obtained by reacting ethylene carbonate and dimethylamine is able to dissolve or disperse a wide range of biocides 20% better than solvents known from the state of the art. Adding oil components as co-solvents, especially those having an ester structure to the compositions lead to emulsifiable concentrates formulations showing increased emulsion behaviour and stability, in particular with respect to opacity and layering. Carbamates

In one or more embodiments, carbamates (component a) according to the present invention (component a) are derived from a reaction of carbonates and amines. The preparation of carbamates is well known from the state of the art. For example, an amine (1.05 moles) is charged into a four neck flask and spurged with a current nitrogen flow during the whole reaction. After reaching a temperature of 45° C., for example a cyclic or alicyclic carbonate (1 mole) is added drop wise while stirring the content of the flask at about 120 rpm. The addition rate has to be adjusted so that the reaction temperature does not exceed 60° C. After complete addition of the carbonate the content of the flask is heated up to 60° C. The reaction is followed by means of the amine value which is determined by titration. After a constant amine value is reached the excess of amine is stripped by vacuum distillation. After distillation the amine value is about zero. Typically, the carbamates follow general formula (II), R²R³—N—(C═O)O—R¹  (II) in which R¹ stands for HO(CH₂)_(n) or CH₃(CH₂)_(m)OH, m and n both represent independently integers of 3 to 22, R² and R³ independently represent hydrogen or alkyl groups having 1 to 12 carbon atoms, optionally forming a ring system.

In a specific embodiment, the carbamates are derived from ethylene carbonate and propylene carbonates. These carbamates exhibit excellent performance in dissolving or dispersing a wide number of different biocides over a long period and both at low and high temperatures, especially when reacted with dimethylamine or morpholine.

Biocides

A biocide (component b) in the context of the present invention is a plant protection agent, more particular a chemical substance capable of killing different forms of living organisms used in fields such as medicine, agriculture, forestry, and mosquito control. Also counted under the group of biocides are so-called plant growth regulators. Usually, biocides are divided into two sub-groups:

-   -   pesticides, which includes fungicides, herbicides, insecticides,         algicides, moluscicides, miticides and rodenticides, (here, The         Pesticide Manual, 14^(th) edition, BCPC 2006 is included as a         reference, it provides information about the individual mode of         actions of active ingredients) and     -   antimicrobials, which includes germicides, antibiotics,         antibacterials, antivirals, antifungals, antiprotozoals and         antiparasites.

Biocides can also be added to other materials (typically liquids) to protect the material from biological infestation and growth. For example, certain types of quaternary ammonium compounds (quats) can be added to pool water or industrial water systems to act as an algicide, protecting the water from infestation and growth of algae.

Pesticides

The U.S. Environmental Protection Agency (EPA) defines a pesticide as “any substance or mixture of substances intended for preventing, destroying, repelling, or mitigating any pest”. A pesticide may be a chemical substance or biological agent (such as a virus or bacteria) used against pests including insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms) and microbes that compete with humans for food, destroy property, spread disease or are a nuisance. In the following examples, pesticides suitable for the agrochemical compositions according to the present invention are given:

Fungicides. A fungicide is one of three main methods of pest control—the chemical control of fungi in this case. Fungicides are chemical compounds used to prevent the spread of fungi in gardens and crops. Fungicides are also used to fight fungal infections. Fungicides can either be contact or systemic. A contact fungicide kills fungi when sprayed on its surface. A systemic fungicide has to be absorbed by the fungus before the fungus dies. Examples for suitable fungicides, according to the present invention, encompass the following chemical classes and corresponding examples:

-   -   Aminopyrimidines such as bupirimate,     -   Anilinopyrimidines such as cyprodinil, mepanipyrim,         pyrimethanil,     -   Heteroaromatics such as hymexazol,     -   Heteroaromatic hydrocarbons such as etridiazole,     -   Chlorophenyls/Nitroanilines such as chloroneb, dicloran,         quintozene, tecnazene, tolclofos-methyl,     -   Benzamide fungicides such as zoxamide,     -   Benzenesulfonamides such as flusulfamide,     -   Benzimidazoles such as acibenzolar, benomyl, benzothiazole,         carbendazim, fuberidazole, metrafenone, probenazole,         thiabendazole, triazoxide, and benzimidazole precursor         fungicides,     -   Carbamates such as propamocarb, diethofencarb,     -   Carboxamides such as boscalid, diclocymet, ethaboxam,         flutolanil, penthiopyrad, thifluzamide     -   Chloronitriles such chlorothalonil,     -   Cinnamic acid amides such as dimethomorph, flumorph,     -   Cyanoacetamide oximes such as cymoxanil,     -   Cyclopropancarboxamides such as carpropamid,     -   Dicarboximides such as iprodione, octhilinone, procymidone,         vinclozolin     -   Dimethyldithiocarbamates such ferbam, metam, thiram, ziram,     -   Dinitroanilines such as fluazinam,     -   Dithiocarbamates such as mancopper, mancozeb, maneb, metiram,         nabam, propineb, zineb,     -   Dithiolanes such as isoprothiolane,     -   Glucopyranosyl antibiotics such as streptomycin, validamycin,     -   Guanidines such as dodine, guazatine, iminoctadine,     -   Hexopyranosyl antibiotics such as kasugamycin,     -   Hydroxyanilides such as fenhexamid,     -   Imidazoles such as imazalil, oxpoconazole, pefurazoate,         prochloraz, triflumizole,     -   Imidazolinones such as fenamidone,     -   Inorganics such as Bordeaux mixture, copper hydroxide, copper         naphthenate, copper oleate, copper oxychloride, copper(II)         sulfate, copper sulfate, copper(II) acetate, copper(II)         carbonate, cuprous oxide, sulfur,     -   Isobenzofuranones such as phthalide,     -   Mandelamides such as mandipropamide,     -   Morpholines such as dodemorph, fenpropimorph, tridemorph,         fenpropidin, piperalin, spiroxamine, aldimorph     -   Organotins such as fentin,     -   Oxazolidinones such as oxadixyl,     -   Phenylamides such as benalaxyl, benalaxyl-M, furalaxyl,         metalaxyl, metalaxyl-M, ofurace,     -   Phenylpyrazoles such as fipronil,     -   Phenylpyrroles such as fludioxonil,     -   Phenylureas such as pencycuron,     -   Phosphonates such fosetyl,     -   Phthalamic acids such as tecloftalam,     -   Phthalimides such as captafol, captan, folpet,     -   Piperazines such as triforine,     -   Propionamides such as fenoxanil,     -   Pyridines such as pyrifenox,     -   Pyrimidines such as fenarimol, nuarimol,     -   Pyrroloquinolinones such as pyroquilon,     -   Qils such as cyazofamid,     -   Quinazolinones such as proquinazid,     -   Quinolines such as quinoxyfen,     -   Quinones such as dithianon,     -   Sulfamides such as tolylfluanid, dichlofluanid,     -   Strobilurines such as azoxystrobin, dimoxystrobin, famoxadone,         fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin,         pyraclostrobin, trifloxystrobin, orysastrobin,     -   Thiocarbamates such as methasulfocarb,     -   Thiophanates such as thiophanate-methyl,     -   Thiophencarboxamides such silthiofam,     -   Triazole fungicides such as azaconazole, bitertanol,         bromuconazole, cyproconazole, difenoconazole, diniconazole,         epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,         flutriafol, fluotrimazole, hexaconazole, imibenconazole,         ipconazole, metconazole, myclobutanil, penconazole,         propiconazole, prothioconazole, simeconazole, tebuconazole,         tetraconazole, triadimefon, triadimenol, triticonazole,         quinconazole     -   Triazolobenzothidazoles such as tricyclazole,     -   Valinamide carbamates such as iprovalicarb, benthiavalicarb     -   Fluopicolide     -   Pentachlorophenol         and their mixtures.

Herbicides. An herbicide is a pesticide used to kill unwanted plants. Selective herbicides kill specific targets while leaving the desired crop relatively unharmed. Some of these act by interfering with the growth of the weed and are often based on plant hormones. Herbicides used to clear waste ground are nonselective and kill all plant material with which they come into contact. Herbicides are widely used in agriculture and in landscape turf management. They are applied in total vegetation control (TVC) programs for maintenance of highways and railroads. Smaller quantities are used in forestry, pasture systems, and management of areas set aside as wildlife habitat. In general, active ingredients representing including various chemical classes and corresponding examples can be used

-   -   Anilides such as propanil     -   Aryloxycarboxylic acids e.g. MCPA-thioethyl     -   Aryloxyphenoxypropionates e.g. clodinafop-propargyl,         cyhalofop-butyl, diclofops, fluazifops, haloxyfops, quizalofops,     -   Chloroacetamides e.g. acetolochlor, alachlor, butachlor,         dimethenamid, metolachlor, propachlor     -   Cyclohexanedione oximes e.g. clethodim, sethoxydim, tralkoxydim,     -   Benzamides such as isoxaben     -   Benzimidazoles such as dicamba, ethofumesate     -   Dinitroanilines e.g. trifluralin, pendimethalin,     -   Diphenyl ethers e.g. aclonifen, oxyfluorfen,     -   The glycine derivative glyphosate, a systemic nonselective (it         kills any type of plant) herbicide used in no-till burndown and         for weed control in crops that are genetically modified to         resist its effects,     -   Hydroxybenzonitriles e.g. bromoxynil,     -   Imidazolinones e.g. fenamidone, imazapic, imazamox, imazapic,         imazapyr, imazaquin,     -   Isoxazolidinones e.g. clomazone     -   Paraquat as bypyridylium,     -   Phenyl carbamates e.g. desmedipham, phenmedipham,     -   Phenylpyrazoles e.g. pyraflufen-ethyl     -   Phenylpyrazolines e.g. pinoxaden,     -   Pyridinecarboxylic acids or synthetic auxins e.g. picloram,         clopyralid, and triclopyr,     -   Pyrimidinyloxybenzoics e.g. bispyrtbac-sodium     -   Sulfonyureas e.g. amidosulfuron, azimsulfuron,         bensulfuron-methyl, chlorsulfuron, flazasulfuron, foramsulfuron,         flupyrsulfuron-methyl-sodium, nicosulfuron, rimsulfuron,         sulfosulfuron, tribenuron-methyl, trifloxysurlfuron-sodium,         triflusulfuron, tritosulfuron,     -   Triazolopyrimidines e.g. penoxsulam, metosulam, florasulam,     -   Triketones e.g. mesotriones, sulcotrione,     -   Ureas e.g. diuron, linuron,     -   Phenoxycarboxylic acids such as 2,4-D, MCPA, MCPB, mecoprops,     -   Triazines such as atrazine, simazine, terbuthylazine,         and their mixtures.

Insecticides. An insecticide is a pesticide used against insects in all developmental forms. They include ovicides and larvicides used against the eggs and larvae of insects. Insecticides are used in agriculture, medicine, industry and the household. In the following, suitable chemical classes and examples of insecticides are mentioned:

-   -   Abamectin, emamectin,     -   Anthranilic diamides such as rynaxypyr     -   Synthetic auxins Duch as avermectin,     -   Amidines such as amitraz,     -   Anthranilic diamide Duch as rynaxypyr,     -   Carbamates such as aldicarb, carbofuran, carbaryl, methomyl,         2-(1-methylpropyl)phenyl methylcarbamate,     -   Chlorinated insecticides such as, for example, Camphechlor, DDT,         Hexachlorocyclohexane, gamma-Hexachlorocyclohexane,         Methoxychlor, Pentachlorophenol, TDE, Aldrin, Chlordane,         Chlordecone, Dieldrin, Endosulfan, Endrin, Heptachlor, Mirex,     -   Juvenile hormone mimics such as pyriproxyfen,     -   Neonicotinoids such as imidacloprid, clothianidin, thiacloprid,         thiamethoxam,     -   Organophosphorus compounds such as acephate, azinphos-methyl,         bensulide, chlorethoxyfos, chlorpyrifos, chlorpyriphos-methyl,         diazinon, dichlorvos (DDVP), dicrotophos, dimethoate,         disulfoton, dthoprop, fenamiphos, fenitrothion, fenthion,         fosthiazate, malathion, methamidophos, methidathion,         methyl-parathion, mevinphos, naled, omethoate,         oxydemeton-methyl, parathion, phorate, phosalone, phosmet,         phostebupirim, pirimiphos-methyl, profenofos, terbufos,         tetrachlorvinphos, tribufos, trichlorfon,     -   Oxadiazines such as indoxacarb,     -   Plant toxin derived compounds such as derris (rotenone),         pyrethrum, neem (azadirachtin), nicotine, caffeine,     -   Pheromones such cuellure, methyl eugenol,     -   Pyrethroids such as, for example, allethrin, bifenthrin,         deltamethrin, permethrin, resmethrin, sumithrin, tetramethrin,         tralomethrin, transfluthrin,     -   Selective feeding blockers such as flonicamid, pymetrozine,     -   Spinosyns e.g. spinosad         and their mixtures.

Plant Growth Regulators. Plant hormones (also known as phytohormones) are chemicals that regulate plant growth. Plant hormones are signal molecules produced within the plant, and occur in extremely low concentrations. Hormones regulate cellular processes in targeted cells locally and when moved to other locations, in other locations of the plant. Plants, unlike animals, lack glands that produce and secrete hormones. Plant hormones shape the plant, affecting seed growth, time of flowering, the sex of flowers, senescence of leaves and fruits. They affect which tissues grow upward and which grow downward, leaf formation and stem growth, fruit development and ripening, plant longevity and even plant death. Hormones are vital to plant growth and lacking them, plants would be mostly a mass of undifferentiated cells. In the following, suitable plant growth regulators are mentioned:

-   -   Aviglycine,     -   Cyanamide,     -   Gibberellins such gibberellic acid,     -   Quaternary ammoniums such as chlormequat chloride, mepiquat         chloride,     -   Ethylene generators such ethephone,

Rodenticides. Rodenticides are a category of pest control chemicals intended to kill rodents. Rodents are difficult to kill with poisons because their feeding habits reflect their place as scavengers. They would eat a small bit of something and wait, and if they do not get sick, they would continue eating. An effective rodenticide must be tasteless and odorless in lethal concentrations, and have a delayed effect. In the following, examples for suitable rodenticides are given:

-   -   Anticoagulants are defined as chronic (death occurs after 1-2         weeks post ingestion of the lethal dose, rarely sooner),         single-dose (second generation) or multiple dose (first         generation) cumulative rodenticides. Fatal internal bleeding is         caused by lethal dose of anticoagulants such as brodifacoum,         coumatetralyl or warfarin. These substances in effective doses         are antivitamins K, blocking the enzymes         K₁-2,3-epoxide-reductase (this enzyme is preferentially blocked         by 4-hydroxycoumarin/4-hydroxythiacoumarin derivatives) and         K₁-quinone-reductase (this enzyme is preferentially blocked by         indandione derivatives), depriving the organism of its source of         active vitamin K₁. This leads to a disruption of the vitamin K         cycle, resulting in an inability of production of essential         blood-clotting factors (mainly coagulation factors II         (prothrombin), VII (proconvertin), IX (Christmas factor) and X         (stuart factor)). In addition to this specific metabolic         disruption, toxic doses of         4-hydroxycoumarin/4-hydroxythiacoumarin and indandione         anticoagulants are causing damage to tiny blood vessels         (capillaries), increasing their permeability, causing diffuse         internal bleedings (haemorrhagias). These effects are gradual;         they develop in the course of days and are not accompanied by         any nociceptive perceptions, such as pain or agony. In the final         phase of intoxication the exhausted rodent collapses in         hypovolemic circulatory shock or severe anemia and dies calmly.         Rodenticidal anticoagulants are either first generation agents         (4-hydroxycoumarin type: warfarin, coumatetralyl; indandione         type: pindone, diphacinone, chlorophacinone), generally         requiring higher concentrations (usually between 0.005 and         0.1%), consecutive intake over days in order to accumulate the         lethal dose, poor active or inactive after single feeding and         less toxic than second generation agents, which are derivatives         of 4-hydroxycoumarin (difenacoum, brodifacoum, bromadiolone and         flocoumafen) or 4-hydroxy-1-benzothiin-2-one         (4-hydroxy-1-thiacoumarin, sometimes incorrectlly referred to as         4-hydroxy-1-thiocoumarin, for reason see heterocyclic         compounds), namely difethialone. Second generation agents are         far more toxic than first generation agents, they are generally         applied in lower concentrations in baits (usually in the order         of 0.001-0.005%), and are lethal after single ingestion of bait         and are effective also against strains of rodents that have         become resistant against first generation anticoagulants; thus         the second generation anticoagulants are sometimes referred to         as “superwarfarins”. Sometimes, anticoagulant rodenticides are         potentiated by an antibiotic, most commonly by sulfaquinoxaline.         The aim of this association (e.g. warfarin         0.05%+sulfaquinoxaline 0.02%, or difenacoum         0.005%+sulfaquinoxaline 0.02% etc.) is that the         antibiotic/bacteriostatic agent suppresses intestinal/gut         symbiotic microflora that represents a source of vitamin K. Thus         the symbiotic bacteria are killed or their metabolism is         impaired and the production of vitamin K by them is diminuted,         an effect which logically contributes to the action of         anticoagulants. Antibiotic agents other than sulfaquinoxaline         may be used, for example co-trimoxazole, tetracycline, neomycin         or metronidazole. A further synergism used in rodenticidal baits         is that of an association of an anticoagulant with a compound         with vitamin D-activity, i.e. cholecalciferol or ergocalciferol         (see below). A typical formula used is, e.g., warfarin         0.025-0.05%+cholecalciferol 0.01%. In some countries there are         even fixed three-component rodenticides, i.e.         anticoagulant+antibiotic+vitamin D, e.g. difenacoum         0.005%+sulfaquinoxaline 0.02%+cholecalciferol 0.01%.         Associations of a second-generation anticoagulant with an         antibiotic and/or vitamin D are considered to be effective even         against the most resistant strains of rodents, though some         second generation anticoagulants (namely brodifacoum and         difethialone), in bait concentrations of 0.0025-0.005% are so         toxic that no known resistant strain of rodents exists and even         rodents resistant against any other derivatives are reliably         exterminated by application of these most toxic anticoagulants.         -   Vitamin K₁ has been suggested and successfully used as an             antidote for pets or humans, which/who were either             accidentally or intentionally (poison assaults on pets,             suicidal attempts) exposed to anticoagulant poisons. In             addition, since some of these poisons act by inhibiting             liver functions and in progressed stages of poisoning,             several blood-clotting factors as well as the whole volume             of circulating blood lacks, a blood transfusion (optionally             with the clotting factors present) can save a person's life             who inadvertently takes them, which is an advantage over             some older poisons.     -   Metal phosphides have been used as a means of killing rodents         and are considered single-dose fast acting rodenticides (death         occurs commonly within 1-3 days after single bait ingestion). A         bait consisting of food and a phosphide (usually zinc phosphide)         is left where the rodents can eat it. The acid in the digestive         system of the rodent reacts with the phosphide to generate the         toxic phosphine gas. This method of vermin control has possible         use in places where rodents are resistant to some of the         anticoagulants, particularly for control of house and field         mice; zinc phosphide baits are also cheaper than most         second-generation anticoagulants, so that sometimes, in cases of         large infestation by rodents, their population is initially         reduced by copious amounts of zinc phosphide bait applied, and         the rest of the population that survived the initial fast-acting         poison is then eradicated by prolonged feeding on anticoagulant         bait. Inversely, the individual rodents that survived         anticoagulant bait poisoning (rest population) can be eradicated         by pre-baiting them with nontoxic bait for a week or two (this         is important to overcome bait shyness, and to get rodents used         to feeding in specific areas by offering specific food,         especially when eradicating rats) and subsequently applying         poisoned bait of the same sort as used for pre-baiting until all         consumption of the bait ceases (usually within 2-4 days). These         methods of alternating rodenticides with different modes of         action provides a factual or an almost 100% eradication of the         rodent population in the area if the acceptance/palatability of         bait is good (i.e., rodents readily feed on it).     -   Phosphides are rather fast acting rat poisons, resulting in that         the rats are dying usually in open areas instead of the affected         buildings. Typical examples are aluminum phosphide (fumigant         only), calcium phosphide (fumigant only), magnesium phosphide         (fumigant only) and zinc phosphide (in baits). Zinc phosphide is         typically added to rodent baits in amounts of around 0.75-2%.         The baits have a strong, pungent garlic-like odor characteristic         for phosphine liberated by hydrolysis. The odor attracts (or, at         least, does not repulse) rodents, but has a repulsive effect on         other mammals; birds, however (notably wild turkeys), are not         sensitive to the smell and feed on the bait thus becoming         collateral damage.     -   Hypercalcemia. Calciferols (vitamins D), cholecalciferol         (vitamin D₃) and ergocalciferol (vitamin D₂) are used as         rodenticides, which are toxic to rodents for the same reason         that they are beneficial to mammals: they are affecting calcium         and phosphate homeostasis in the body. Vitamins D are essential         in minute quantities (few IUs per kilogram body weight daily,         which is only a fraction of a milligram), and like most fat         soluble vitamins they are toxic in larger doses as they readily         result in the so-called hypervitaminosis, which is, simply said,         poisoning by the vitamin. If the poisoning is severe enough         (that is, if the dose of the toxicant is high enough), it         eventually leads to death. In rodents consuming the rodenticidal         bait it causes hypercalcemia by raising the calcium level,         mainly by increasing calcium absorption from food, mobilising         bone-matrix-fixed calcium into ionised form (mainly         monohydrogencarbonate calcium cation, partially bound to plasma         proteins, [CaHCO₃]⁺), which circulates dissolved in the blood         plasma, and after ingestion of a lethal dose the free calcium         levels are raised sufficiently so that blood vessels, kidneys,         the stomach wall and lungs are mineralised/calcificated         (formation of calcificates, crystals of calcium salts/complexes         in the tissues thus damaging them), leading further to heart         problems (myocard is sensitive to variations of free calcium         levels that are affecting both myocardial contractibility and         excitation propagation between atrias and ventriculas) and         bleeding (due to capillary damage) and possibly kidney failure.         It is considered to be single-dose, or cumulative (depending on         concentration used; the common 0.075% bait concentration is         lethal to most rodents after a single intake of larger portions         of the bait), sub-chronic (death occurring usually within days         to one week after ingestion of the bait). Applied concentrations         are 0.075% cholecalciferol and 0.1% ergocalciferol when used         alone. There is an important feature of calciferols toxicology         which is that they are synergistic with anticoagulant toxicants.         This means that mixtures of anticoagulants and calciferols in         the same bait are more toxic than the sum of toxicities of the         anticoagulant and the calciferol in the bait so that a massive         hypercalcemic effect can be achieved by a substantially lower         calciferol content in the bait and vice-versa. More pronounced         anticoagulant/hemorrhagic effects are observed if calciferol is         present. This synergism is mostly used in baits low in         calciferol because effective concentrations of calciferols are         more expensive than effective concentrations of most         anticoagulants. The historically very first application of a         calciferol in rodenticidal bait was, in fact, the Sorex product         Sorexa® D (with a different formula than today's Sorexa® D) back         in the early 1970's, containing warfarin 0.025%+ergocalciferol         0.1%. Today, Sorexa® CD contains a 0.0025% difenacoum+0.075%         cholecalciferol combination. Numerous other brand products         containing either calciferols 0.075-0.1% (e.g. Quintox®,         containing 0.075% cholecalciferol) alone, or a combination of         calciferol 0.01-0.075% with an anticoagulant are marketed.

Miticides, Moluscicides and Nematicides. Miticides are pesticides that kill mites. Antibiotic miticides, carbamate miticides, formamidine miticides, mite growth regulators, organochlorine, permethrin and organophosphate miticides all belong to this category. Molluscicides are pesticides used to control mollusks, such as moths, slugs and snails. These substances include metaldehyde, methiocarb and aluminium sulfate. A nematicide is a type of chemical pesticide used to kill parasitic nematodes (a phylum of worm). A nematicide is obtained from a neem tree's seed cake; which is the residue of neem seeds after oil extraction. The neem tree is known by several names in the world but was first cultivated in India since ancient times.

Antimicrobials

In the following examples, antimicrobials suitable for agrochemical compositions according to the present invention are given. Bactericidal disinfectants mostly used are those applying

-   -   active chlorine (i.e., hypochlorites, chloramines,         dichloroisocyanurate and trichloroisocyanurate, wet chlorine,         chlorine dioxide, etc.),     -   active oxygen (peroxides such as peracetic acid, potassium         persulfate, sodium perborate, sodium percarbonate and urea         perhydrate),     -   iodine (iodpovidone (povidone-iodine, Betadine), Lugol's         solution, iodine tincture, iodinated nonionic surfactants),     -   concentrated alcohols (mainly ethanol, 1-propanol, called also         n-propanol and 2-propanol, called isopropanol and mixtures         thereof; further, 2-phenoxyethanol and 1- and 2-phenoxypropanols         are used),     -   phenolic substances (such as phenol (also called “carbolic         acid”), cresols (called “Lysole” in combination with liquid         potassium soaps), halogenated (chlorinated, brominated) phenols,         such as hexachlorophene, triclosan, trichlorophenol,         tribromophenol, pentachlorophenol, Dibromol and salts thereof),     -   cationic surfactants such as some quaternary ammonium cations         (such as benzalkonium chloride, cetyl trimethylammonium bromide         or chloride, didecyldimethylammonium chloride, cetylpyridinium         chloride, benzethonium chloride) and others, non-quarternary         compounds such as chlorhexidine, glucoprotamine, octenidine         dihydrochloride, etc.),     -   strong oxidizers such as ozone and permanganate solutions;     -   heavy metals and their salts such as colloidal silver, silver         nitrate, mercury chloride, phenylmercury salts, copper sulfate,         copper oxide-chloride etc. Heavy metals and their salts are the         most toxic and environmentally hazardous bactericides and,         therefore, their use is strongly suppressed or forbidden;         further, also     -   properly concentrated strong acids (phosphoric, nitric,         sulfuric, amidosulfuric, toluenesulfonic acids) and     -   alcalis (sodium, potassium, calcium hydroxides) between pH<1         or >13, particularly below elevated temperatures (above 60° C.)         kill bacteria.

As antiseptics (i.e., germicide agents that can be used on human or animal body, skin, mucoses, wounds and the like), few of the above mentioned disinfectants can be used under proper conditions (mainly concentration, pH, temperature and toxicity toward man/animal). Among them, important are

-   -   some properly diluted chlorine preparations (e.g. Daquin's         solution, 0.5% sodium or potassium hypochlorite solution,         pH-adjusted to pH 7-8, or 0.5-1% solution of sodium         benzenesulfochloramide (chloramine B)), some     -   iodine preparations such as iodopovidone in various galenics         (ointments, solutions, wound plasters), in the past also Lugol's         solution,     -   peroxides as urea perhydrate solutions and pH-buffered 0.1-0.25%         peracetic acid solutions,     -   alcohols with or without antiseptic additives, used mainly for         skin antisepsis,     -   weak organic acids such as sorbic acid, benzoic acid, lactic         acid and salicylic acid     -   some phenolic compounds such as hexachlorophene, triclosan and         Dibromol, and     -   cation-active compounds such as 0.05-0.5% benzalkonium, 0.5-4%         chlorhexidine, 0.1-2% octenidine solutions.

Bactericidal antibiotics kill bacteria; bacteriostatic antibiotics only slow down their growth or reproduction. Penicillin is a bactericide, as are cephalosporins. Aminoglycosidic antibiotics can act in both a bactericidic manner (by disrupting cell wall precursor leading to lysis) or bacteriostatic manner (by connecting to 30s ribosomal subunit and reducing translation fidelity leading to inaccurate protein synthesis). Other bactericidal antibiotics according to the present invention include the fluoroquinolones, nitrofurans, vancomycin, monobactams, co-trimoxazole, and metronidazole Preferred actives are those with systemic or partially systemic mode of action such as for example azoxystrobin.

In a specific embodiment, the biocides are selected from the group consisting of azoles, oxyfluorfen, propanil, chlorpyrifos, bifenthrin, novaluron, phenmedipham, deltamethrin, acetochlore, lambdacyhalothrin, glyphosate and its salts, glufosinate and its salts, and mixtures of these species.

Oil Components/Co-solvents

Suitable oil components (component c) are, for example, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear or branched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl emcate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of linear C₆-C₂₂-fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of C₁₈-C₃₈-alkylhydroxy carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, in particular Dioctyl Malate, esters of linear and/or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimertriol) and/or Guerbet alcohols, triglycerides based on C₆-C₁₀-fatty acids, liquid mono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters of C₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C₂-C₁₂-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms (Cetiol® B) or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C₆-C₂₂-fatty alcohol carbonates, such as, for example, Dicaprylyl Carbonate (Cetiol® CC), Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C₆-C₂₂-alcohols (e.g. Cetiol® AB), linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, such as, for example, dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicones, silicone methicone grades, etc.), aliphatic or naphthenic hydrocarbons, such as, for example, squalane, squalene or dialkylcyclohexanes, and/or mineral oils.

In a one or more embodiments of the present invention, the oil components/co-solvents have an ester structure. In a specific embodiment, the oil component/co-solvent is selected from adipates (Cetiol® B, Agnique® DiME 6), methyl esters of vegetable oils (Agnique ME 18RD-F, Agnique® ME 12C-F), alkyl esters (Agnique® Ae 3-2EH=2-EthylHexyl Lactate)—all products available in the market from Cognis GmbH, Dusseldorf.

Emulsifiers

Suitable emulsifiers (component d) include non-ionic and anionic surfactants and their mixtures. Non-ionic surfactants include for example:

-   -   products of the addition of 2 to 30 mol ethylene oxide and/or 0         to 5 mol propylene oxide onto linear C₈₋₂₂ fatty alcohols, onto         C₁₂₋₂₂ fatty acids and onto alkyl phenols containing 8 to 15         carbon atoms in the alkyl group;     -   C_(12/18) fatty acid monoesters and diesters of addition         products of 1 to 30 mol ethylene oxide onto glycerol;     -   glycerol mono- and diesters and sorbitan mono- and diesters of         saturated and unsaturated fatty acids containing 6 to 22 carbon         atoms and ethylene oxide addition products thereof;     -   addition products of 15 to 60 mol ethylene oxide onto castor oil         and/or hydrogenated castor oil;     -   polyol esters and, in particular, polyglycerol esters such as,         for example, polyglycerol polyricinoleate, polyglycerol         poly-12-hydroxystearate or polyglycerol dimerate isostearate.         Mixtures of compounds from several of these classes are also         suitable;     -   addition products of 2 to 15 mol ethylene oxide onto castor oil         and/or hydrogenated castor oil;     -   partial esters based on linear, branched, unsaturated or         saturated C₆/22 fatty acids, ricinoleic acid and         12-hydroxystearic acid and glycerol, polyglycerol,         pentaerythritol, -dipentaerythritol, sugar alcohols (for example         sorbitol), alkyl glucosides (for example methyl glucoside, butyl         glucoside, lauryl glucoside) and polyglucosides (for example         cellulose);     -   mono-, di and trialkyl phosphates and mono-, di- and/or         tri-PEG-alkyl phosphates and salts thereof;     -   wool wax alcohols;     -   polysiloxane/polyalkyl polyether copolymers and corresponding         derivatives;     -   mixed esters of pentaerythritol, fatty acids, citric acid and         fatty alcohol and/or mixed esters of C₆₋₂₂ fatty acids, methyl         glucose and polyols, preferably glycerol or polyglycerol,     -   polyalkylene glycols and

The addition products of ethylene oxide and/or propylene oxide onto fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or onto castor oil are known commercially available products. They are homologue mixtures of which the average degree of alkoxylation corresponds to the ratio between the quantities of ethylene oxide and/or propylene oxide and substrate with which the addition reaction is carried out. C_(12/18) fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known as lipid layer enhancers for cosmetic formulations. The emulsifiers according to one or more embodiments are described in more detail as follows:

Partial Glycerides

Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, tartaric acid diglyceride, citric acid monoglyceride, citric acid diglyceride, malic acid monoglyceride, malic acid diglyceride and technical mixtures thereof which may still contain small quanti-ties of triglyceride from the production process. Addition products of 1 to 30, and preferably 5 to 10, mol ethylene oxide onto the partial glycerides mentioned are also suitable.

Sorbitan Esters

Suitable sorbitan esters are sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxyystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate and technical mixtures thereof. Addition products of 1 to 30, and preferably 5 to 10, mol ethylene oxide onto the sorbitan esters mentioned are also suitable.

Alk(en)yl Oligoglycosides

In one or more embodiments, the emulsifier is selected from alkyl or alkenyl oligoglycosides, which may be derived from aldoses or ketoses containing 5 or 6 carbon atoms, preferably glucose. Accordingly, in a specific embodiment, the alkyl and/or alkenyl oligoglycosides are alkyl or alkenyl oligoglucosides. These materials are also known generically as “alkyl polyglycosides” (APG). The alk(en)yl oligoglycosides according to the invention correspond to formula (III): R⁴O[G]_(p)  (III) wherein R⁴ is an alkyl or alkenyl radical having from 6 to 22 carbon atoms, G is a sugar unit having 5 or 6 carbon atoms and p is a number from 1 to 10. The index p in general formula (II) indicates the degree of oligomerisation (DP degree), i.e. the distribution of mono- and oligoglycosides, and is a number of 1 to 10. Whereas p in a given compound must always be an integer and, above all, may assume a value of 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined calculated quantity which is mostly a broken number. Alk(en)yl oligoglycosides having an average degree of oligomerisation p of 1.1 to 3.0 are preferably used. Alk(en)yl oligoglycosides having a degree of oligomerisation below 1.7 and, more particularly, between 1.2 and 1.4 are preferred from the applicational point of view. The alkyl or alkenyl radical R⁵ may be derived from primary alcohols containing 4 to 22 and preferably 8 to 16 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereof such as are formed, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Alkyl oligoglucosides based on hydrogenated C₈-C₁₆ coconut oil alcohol having a DP of 1 to 3 are preferred. Also suitable are alkoxylation products of alkyl oligoglucosides, for example adducts of 1 to 10 moles ethylene oxide and/or 1 to 5 moles propylene oxide to C₈-C₁₀ or C₁₂-C₁₈ alkyl oligoglucoside having a DP between 1.2 and 1.4. Alkoxylated Vegetable Oils

Suitable emulsifiers are castor oil, rape seed oil, soy been oil ethoxylated with 3 to 80 moles ethylene oxide (Agnique CSO 35, Agnique SBO 10, Agnique SBO 60))

Alkoxylated Copolymers

Typical copolymers are ethoxylated and propoxylated block and/or random polymers of C₂₋₂₂ linear or branched alcohols.

Miscellaneous Emulsifiers

Typical anionic emulsifiers are for example alkylbenzene sulfonates like dodecylbenzene sulfonate salts (e.g. Agnique® ABS 60 C or 65C), di-octyl sulfosuccinates or anionic polymers like polyacrylates. Other suitable emulsifiers are zwitterionic surfactants. Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N,N-dimethyl ammonium glycinates, for example cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for example cocoacylaminopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group and cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. Ampholytic surfactants are also suitable emulsifiers. Ampholytic surfactants are surface-active compounds which, in addition to a C_(8/18) alkyl or acyl group, contain at least one free amino group and at least one —COOH— or —SO₃H— group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C_(12/18) acyl sarcosine.

Biocide Compositions

Depending on the nature of the biocide the products may show the following compositions:

-   (a) about 0.1% b.w. to about 99% b.w., preferably about 15% b.w. to     about 70% b.w., and most preferably about 20% b.w. to about 45%     b.w., carbamates, -   (b) about 1% b.w. to about 99.1% b.w., preferably about 5% b.w. to     about 75% b.w., and most preferably about 15% b.w. to about 40%     b.w., biocides, -   (c) 0 to about 50 b.w., preferably about 5% b.w. to about 30% b.w.     and more preferably about 10% b.w. to about 25% b.w. oil     components/co-solvents and -   (d) 0 to about 15% b.w., and preferably about 5% b.w. to about 10%     b.w., emulsifiers

On the condition that the numbers optionally together with water add to 100% b.w. The compositions represent concentrates to be diluted with water to give aqueous formulations for end-users comprising about 0.5 to about 5, preferably about 0.5 to about 1% of the active matter represented by the concentrate.

Industrial Application

A final embodiment of the present invention is related to the use of carbamates, in particular carbamates derived from ethylene carbonate and propylene carbonate as green solvents or dispersants for biocides.

EXAMPLES Examples 1 to 4 Stability

Several Emulsifiable Concentrates (“EC”) have been designed and prepared by mixing biocides, carbamates, co-solvents and emulsifiers. The concentrates were subsequently diluted at 5% in water. Characteristics of 5 b.w. emulsions in different water hardness and stored at 20° C. for 24 h were assessed. The stability of the emulsions was determined as a function of time. As far as layering is concerned (++) means “no layering” and (+) “about 1 ml layering”. For opacity (++) means an opaque white emulsion and (+) a slightly opalescent emulsion.

TABLE 1 Stability of biocide compositions Composition [% b.w.] 1 2 3 4 Tebuconazole 20 20 20 20 Carbamate from ethylene carbonate + DMA 35 40 — — Carbamate from propylene carbonate + — — 35 40 DMA Dibutyl Adipate — 10 10 2-Ethylhexyl Lactate 35 20 35 20 Saccharose derivative 10 — 10 Agnique ® MBL 510 —  6 —  7 Agnique ® MBL 520 —  4 —  3 Appearance Clear Clear Clear Clear Emulsion properties spontaneously ++ ++ + ++ layering after 1 h ++ ++ ++ ++ opacity after 1 h ++ ++ + + layering after 2 h + + ++ ++ opacity after 2 h ++ ++ + + layering after 24 h + + + +

The examples indicate that excellent emulsification behaviour is obtained as a result of optimized solvents mixture and emulsifier systems.

Examples 5 to 11 Comparative Example C1 Solubility

Solubility of two fungicides, one herbicide and two insecticides in different dialkyl amides at 25° C. was tested. The results, including minimum target solubility for each biocide is presented in Table 2.

TABLE 2 Solubility of biocides [% b.w.] Ex. Solvents Tebucanozole Epoxiconazole 5 Carbamate from EC + DMA 27 12 6 Carbamate from PC + DMA 27  9 7 Carbamate from EC + butyl amine 20 — 8 Carbamate from EC + propyl 23 — amine 9 Carbamate from PC + butyl amine 20 — 10 Carbamate from BC + DMA 30 — 11 Carbamate from BC + pyrrolidone 40 — C1 2-Ethylhexyl Lactate 25  8 EC = Ethylene Carbonate PC = Propylene Carbonate DMA = Dimethyl amine 

What is claimed is:
 1. A biocide composition, comprising: (a) about 15 to about 70% of a carbamate according to formula (I) R²R³—N—(C═O)O—R¹  (I), wherein R¹ represents HO(CH₂)_(n)—, represents an integer of 2 to 22, R² and R³ independently represent hydrogen or alkyl groups having 1 to 12 carbon atoms, optionally forming a ring system, (b) about 5 to about 75% of a biocide, (c) about 5 to 50% of an oil component/co-solvent and (d) about 5 to 15% of an emulsifier, wherein the biocide comprises a fungicide selected from triazoles, and wherein the numbers add optionally together with water to 100%.
 2. The composition of claim 1, wherein R¹ represents HO(CH₂)_(n)— and n represents an integer of 2 or
 3. 3. The composition of claim 1, wherein the oil component/co-solvent is selected from the group consisting of Guerbet alcohols based on fatty alcohols having 6 to 18 carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear or branched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, methyl esters of C₆-C₂₂ fatty acids, esters of linear C₆-C₂₂-fatty acids with branched alcohols, esters of C₁₈-C₃₈ alkyl hydroxy carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols and/or Guerbet alcohols, triglycerides based on C₆-C₁₀-fatty acids, liquid mono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters of C₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, esters of C₂-C₁₂-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C₆-C₂₂-fatty alcohol carbonates, Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of monopropylene glycol with C₂-C₁₈ acids and benzoic acid, esters of benzoic acid with linear and/or branched C₆-C₂₂-alcohols, linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons, mineral oils, and mixtures thereof.
 4. The composition of claim 1, wherein the oil component has an ester structure.
 5. The composition of claim 4, wherein the oil component is selected from the group consisting of adipates, methyl esters of vegetable oils, and alkyl esters.
 6. The composition of claim 1, wherein the emulsifier is selected from non-ionic and/or anionic surfactants.
 7. A method of preparing biocides, the method comprising mixing about 15 to about 70% of a green solvent or disperant comprising a carbamate according to formula (I) R²R³—N—(C═O)O—R¹  (I), wherein R¹ represents HO(CH₂)_(n)—, represents an integer of 2 to 22, R² and R³ independently represent hydrogen or alkyl groups having 1 to 12 carbon atoms, optionally forming a ring system; about 5 to about 75% of a biocide; about 5 to 50% of an oil component; and about 5 to 15% of an emulsifier, wherein the biocide comprises a fungicide selected from triazoles, and wherein the numbers add optionally together with water to 100%.
 8. The method of claim 7, wherein the oil component/co-solvent is selected from the group consisting of Guerbet alcohols based on fatty alcohols having 6 to 18 carbon atoms, esters of linear C₆-C₂₂-fatty acids with linear or branched C₆-C₂₂-fatty alcohols or esters of branched C₆-C₁₃-carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, methyl esters of C₆-C₂₂ fatty acids, esters of linear C₆-C₂₂-fatty acids with branched alcohols, esters of C₁₈-C₃₈ alkyl hydroxy carboxylic acids with linear or branched C₆-C₂₂-fatty alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols and/or Guerbet alcohols, triglycerides based on C₆-C₁₀-fatty acids, liquid mono-/di-/triglyceride mixtures based on C₆-C₁₈-fatty acids, esters of C₆-C₂₂-fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, esters of C₂-C₁₂-dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C₆-C₂₂-fatty alcohol carbonates, Guerbet carbonates, based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of monopropylene glycol with C₂-C₁₈ acids and benzoic acid, esters of benzoic acid with linear and/or branched C₆-C₂₂-alcohols, linear or branched, symmetrical or asymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons, mineral oils, and mixtures thereof.
 9. The method of claim 7, wherein the oil component is selected from the group consisting of adipates, methyl esters of vegetable oils, and alkyl esters.
 10. The method of claim 7, wherein the emulsifier is selected from non-ionic and/or anionic surfactants. 